Azo-dyestuffs and process of making same



Patented July 12, 1932 UNITED STATES PATENT FFIcE,

GERALD BONH6'I'E, 0F BASEL, SWITZERLAND, ASSIGN'OR ,TO THE FIRM OFSOCIETY 01' i CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLANDnzo-nynsrurrs m) rnoonss on MAKING SAME No Drawing. Application filedJuly 14, 1930, Serial No. 467,957, and in Switzerland. July 18, 192% Thepresent invention relates to the manufacture of new azo-dyestuffs whichare particularly valuable for producing fast tints on the fiber. Itcomprises the new products, their process of manufacture, and thematerial which has been dyed with the new products.

According to this invention very valuable new dyestufi's are made bycoupling an arylide of 2:3-hydroxynaphthoic acid with a diazo-compoundof the general formula halogen NH (i=0 i in which w represents halogen,an alkyl-group or an alkoXy-group, and 3 an aryl nucleus of the benzeneseries. The new products, which correspond with the general formulaHN-Jl-Rx halogen if N oo-Nn-nz Y ness and excellent fastness properties,par

ticularly to chlorine and kier boiling.

The following examples illustrate the invention:- v

Example 1 MJEO immediately separates in the form of a red precipitate;this is filtered and dried. It forms a dark red powder.

If the chlorine atom standing in the 5- position of the diazotizingcomponent is replaced by a bromine atom, a similar dyestufi is obtained.V I

Example 2 Cotton yarn is impregnated with a grounding liquor made bydissolving 7 grams of the a-naphthalide of 2: 3-hydroxynaphthoic acid in300 cc. of hotwater with addition ofl5 cc. of caustic soda solution of30 per cent strength and 15 cc. of Turkey red oil, the whole being madeup to 1 litre. The yarn is then Wound oil and developed in a solutionneutralized with sodium acetate and containing l grams of diazotized1-amino-2-methy1- 4-benZoylamino-5-chlorobenzene per litre. There isproduced a pure Bordeaux tint of excellent properties of fastness. Theformula of the formed dyestuff is N OH 0-? a tin. c

replaced by a bromine atom, or theresidue of the benzoic acid by theresidue of another aromatic carboxylic acid, such as achlorobenzoic acidor a paraor meta-alkyloxybenzoic acid, such as para-methoxybenzoic acid.

Example 3 Cotton yarn is impregnated in a bath containing 8 parts ofortho-toluidide of 2 3-hydroxynaphthoic acid per litre. The yarn is,

cautiously wound off and developed in a solution neutralized with sodiumacetate containing 5 grams of diazotized1-amino-2z5-dichloro--benzoylamino-benzene per litre. Very pure red-bluetintsare thus obtained which possess excellent fastness properties tochlorine, to *fulling and to light. The dye- ,stufi' precipitated on thefiber corresponds with the formula -011 NOE? By replacing in thisexample the orthotoluidide of 2: 3-hydroxynaphthoic acid by the metaorthe para-toluidide or also by the para-anisidide, or by the5-chloro-2-toluidide, red dyeings of the same shade are produced,whereas the use of arylides, such as the orthochloranilide or the 2:5-dichloranilide leads to more red-scarlet dyeings. Analogous productsare obtained from diazotizing components in which the chlorine has beenreplaced by one or two bromine atoms.

Example 4 The material to be printed is padded with I an alkalinesolution containing per litre .12 grams of the para-chloro-anilide of 23-hydroxynaphthoic acid. After drying, the mate'rial isprinted with apaste which contains per kilogram 7 grams of diazotized l-methoxy 2amino-l chloro- 5 -benzoylamino-benzene. The deep, pure reddish violetdyestufii' of the formula develops very quickly and is very fast.

In this case also like tints are obtained with other arylides of 23-hydroxynaphthoic acid, such as, for example, the a-naphthylamide, theanilide or the 5-chloro-2-toluidide of the 2 3-hydroxynaphthoic acid.The orthotoluidide, the l-'chloroQ-anisidide and the para-anisidide leadto violets which are somewhat more red. Obviously the combinations ofthis example may be produced on yarn, just as the combinations of thepreceding Examples 1 to 3 may be used for the dyeing of textile fabricsor for printing.

If the l-methoxy-Q-amino-4-chloro-5-benzoylamino-benzene is replaced bycompounds such as, for example, 1-ethoxy-2-amino-4-chloro-5-benzoylamino-benzene or l-ethoxy- 2- amino 4:- chloro: 5-p ara-;methoxy-benzoylamino-benzene, there are also" obtained productsyielding violet shades.

What I claim is a 1. A manufacture of new azo-dyestuf'fs by couplingwith an arylide of 2:3-naphthoic acid ofthe general formula which Rstands for an aryl nucleus of the benzene or of the naphthalene series,a diazocompound of the general formula IF=N-OH 1 halog n in which :20represents halogen, an alkyl-group or an alkoxy-group, and R an arylnucleus of the benzene series.

2. A manufacture of new Bordeaux to vio- I i let azo-dyestuffs bycoupling with an aryllde of 2 3-naphthoic acid of the general formulainwhich R stands for an aryl nucleus of the benzene or of thenaphthalene series, a diazocompound of the general formula halogen inwhich :22 represents an alkylor an alkoxygroup, and R an aryl nucleus ofthe benzene series.

3. A manufacture of new violet azoedyestuffs by coupling with an arylideof 2:3- naphthoic acid of the general formula in which R stands for anaryl nucleus of the benzene or of the naphthalene series, adiazocompound of the general formula halogen in which a; represents analkoxy-group, and

R an aryl nucleus of the benzene series.

4; A manufacture of a new violet azo-dyestuff by coupling thepara-chloranilide of 2: 3-hydroxynaphthoic acid with the diazocompoundof the formula c OCH:

-g@ 5. A manufacture of new azo-dyestufi's by coupling with an arylideof 2:3-naphthoic acid of the general formula in which R stands for anaryl nucleus of the benzene or of the naphthalene series, adiazocompound of the general formula rl r=N on halogen halogen wherein Rstands for an aryl nucleus of the A benzene series.

6. A manufacture of new azo-dyestufi's by coupling with anarylideof-2z3-naphthoic acid of the general formula CO-NH-R:

in which R stands for an aryl nucleus of the benzeneor of thenaphthalene series, a diazocompound of the general formula 8'. 'As newproducts theazodyestufis of the general formula r i w t-0 m halogen I VOH"-"H E ra-LB:

in which w stands for halogen, alkyl or alkoxy, R for an aryl nucleus ofthe benzene series, and R for an aryl nucleus of the benzene or of thenaphthalene series, which products form red Bordeaux and violet powders,yielding, when 'produ cedon the fiber, similar tints which aredistinguished by their vividness and excellent fastness properties,particularly to chlorine and kier boiling.

9. As new products the azo-dyestuffs of the general formula in which :1:stands for alkoxy, R for an aryl nucleus of thebenzene series, and R foran aryl nucleus ofthe benzene or of the naphthalene series, whichproducts form violet powders, yielding, when produced on the fiber,similar tints which are distinguished by their vividness and excellentfastness properties, particularly to chlorine and kier boiling.

11. As a new product the violet azo-dyestuff of the formula whichproduct forms a dark violet powder yielding, when produced on the fiber,pure violet tints which'are distinguished by their vividness andexcellent fastness properties, particularly to chlorine and kierboiling.

12. As new products the azo-dyestuffs of the general formula M a inwhich R stands for an aryl nucleus of the benzene series, and R for anaryl nucleus of the benzene or of the naphthalene series, which productsform red powders yielding, when produced on the fiber, red tints ofgreat vividness which have excellent fastness properties, particularlyto chlorine and kier boilmg. 7 V 7 13. As new products the azo-dyestulfsof the general formula I p in which R stands. for an aryl nucleus of thebenzene series, and R for an aryl nucleus of the benzene or ofthenaphthalene series, 7

which products form red powders yielding,

excellent fastness when produced on the fiber, red tints of greatvividness which have excellent fastness properties, particularly tochlorine and kier boil- 111 34:. As new products the azo-dyestufi's ofthe general formula in which R stands for an aryl nucleus of the benzeneseries which products form blue-red powders yielding, when produced onthe fiber, blue-red tints of great vividness which have properties,particularly to chlorine and kier boiling. e

15. As new products the azo-dyestuffs of the formula N V IL O-N n 1Qwhich products form blue-red powders yielding, when produced on thefiber, blue-red tints of great vividness which have excellent fastnessproperties, particularly to chlorine and kier boiling.

In Witness whereof I have hereunto signed my name this 3rd day of July,1930.

GERALD BONHOTE.

